CN119194901B - Plastic film agent for preventing hot water penetration, preparation method and application thereof in paper mold manufacturing - Google Patents
Plastic film agent for preventing hot water penetration, preparation method and application thereof in paper mold manufacturing Download PDFInfo
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- CN119194901B CN119194901B CN202411707217.6A CN202411707217A CN119194901B CN 119194901 B CN119194901 B CN 119194901B CN 202411707217 A CN202411707217 A CN 202411707217A CN 119194901 B CN119194901 B CN 119194901B
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- hot water
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000002985 plastic film Substances 0.000 title claims description 90
- 229920006255 plastic film Polymers 0.000 title claims description 90
- 239000003795 chemical substances by application Substances 0.000 title claims description 87
- 230000035515 penetration Effects 0.000 title claims description 16
- 230000003405 preventing effect Effects 0.000 title description 33
- 238000000465 moulding Methods 0.000 claims abstract description 93
- 238000006243 chemical reaction Methods 0.000 claims abstract description 78
- 239000007788 liquid Substances 0.000 claims abstract description 77
- 239000000463 material Substances 0.000 claims abstract description 37
- 239000004014 plasticizer Substances 0.000 claims abstract 11
- 238000003756 stirring Methods 0.000 claims description 72
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 60
- 239000008367 deionised water Substances 0.000 claims description 42
- 229910021641 deionized water Inorganic materials 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 239000003607 modifier Substances 0.000 claims description 33
- 230000003014 reinforcing effect Effects 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 29
- 150000001299 aldehydes Chemical class 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 20
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 20
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 19
- 239000005543 nano-size silicon particle Substances 0.000 claims description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 17
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 13
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 10
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 235000010265 sodium sulphite Nutrition 0.000 claims description 10
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 10
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 claims description 10
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 7
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 230000001804 emulsifying effect Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 12
- 230000007774 longterm Effects 0.000 abstract description 8
- 239000012778 molding material Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 description 18
- 239000000178 monomer Substances 0.000 description 17
- 239000000835 fiber Substances 0.000 description 15
- 238000007037 hydroformylation reaction Methods 0.000 description 15
- 239000000123 paper Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 12
- 230000000149 penetrating effect Effects 0.000 description 11
- 229920001131 Pulp (paper) Polymers 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000011436 cob Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229920006254 polymer film Polymers 0.000 description 6
- 235000011888 snacks Nutrition 0.000 description 6
- 230000009172 bursting Effects 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- -1 acrylic ester Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 238000010009 beating Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011087 paperboard Substances 0.000 description 3
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- VFRQEVIIBMUKCQ-UHFFFAOYSA-M ethyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(C)CCOC(=O)C=C VFRQEVIIBMUKCQ-UHFFFAOYSA-M 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 235000003166 Opuntia robusta Nutrition 0.000 description 1
- 244000218514 Opuntia robusta Species 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
- D21J5/00—Manufacture of hollow articles by transferring sheets, produced from fibres suspensions or papier-mâché by suction on wire-net moulds, to couch-moulds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明提供一种防热水渗透的塑膜剂、制备方法及在纸模制造中的应用，属于塑膜剂领域。所述防热水渗透的塑膜剂的制备方法，由以下步骤组成：制备反应底料、制备滴加液、接触反应。本发明的防热水渗透的塑膜剂，能够在避免纸浆模塑掉屑，有效提高纸浆模塑防水性能的同时，有效避免塑膜剂对纸浆模塑的力学性能的影响，进一步改善纸浆模塑的强度和挺度；同时，提高塑膜剂与纸浆模塑材料的结合性能，提高纸浆模塑制品的整体稳定性；以及进一步提高塑膜剂的长期存储稳定性。The present invention provides a hot water-resistant plasticizer, a preparation method and an application in paper mold manufacturing, and belongs to the field of plasticizers. The preparation method of the hot water-resistant plasticizer comprises the following steps: preparing a reaction base material, preparing a drop liquid, and contacting a reaction. The hot water-resistant plasticizer of the present invention can effectively avoid the influence of the plasticizer on the mechanical properties of the pulp molding while avoiding the pulp molding from dropping chips and effectively improving the waterproof performance of the pulp molding, further improving the strength and stiffness of the pulp molding; at the same time, improving the bonding performance of the plasticizer with the pulp molding material, improving the overall stability of the pulp molded product; and further improving the long-term storage stability of the plasticizer.
Description
Technical Field
The invention relates to the field of plastic film agents, in particular to a plastic film agent for preventing hot water from penetrating, a preparation method and application thereof in paper mold manufacturing.
Background
Along with the improvement of the living standard of people and the acceleration of the work rhythm, the disposable snack food container has huge consumption, and particularly the snack food box and the like which are made of the expanded polystyrene as the main raw material have wide application. However, plastic products made of the materials can not be naturally decomposed or recycled, and the waste snack boxes are visible everywhere, so that serious environmental pollution is caused. Environmental pollution is a common concern of society in recent years, development of environment-friendly biomass materials has become a main direction of development of the current green packaging industry, and pulp molded products, which are one of ideal choices for replacing petroleum-based packaging materials, are receiving extensive attention from current researches.
The paper pulp molding is a three-dimensional papermaking technology, adopts primary plant fiber or secondary plant fiber as raw material, has the advantages of rich reserve, recycling, no environmental pollution, natural degradation and the like, and is widely applicable to the fields of snack tableware, food industry buffer packaging and the like. Wherein, the snack tableware comprises a cutlery box, a dinner plate, a dinner bowl, a paper cup and the like, and the food industry buffer package comprises an egg tray, a fruit tray, a food buffer tray and the like. In the specific pulp molding preparation process, bagasse pulp and bamboo pulp are generally used as raw materials, and paper products with specific geometric cavity structures are finally obtained after the processes of pulping, pulp mixing and the like are carried out on a pulp molding machine through the processes of vacuum suction filtration molding, hot pressing drying, shaping and the like of a mold.
Because the main principle component of the pulp molding product is cellulose, a large number of gap structures exist in a fiber network, and the pulp molding product has the defects of easy chip falling and poor waterproof performance, and can not completely meet the performance requirements of snack tableware and the like. In the prior art, the waterproof performance of the pulp molding product is improved by adopting a mode of internal sizing or surface sizing and adopting a plastic film agent.
The existing plastic film agent is used for preparing pulp molding, and can prevent scraps of the pulp molding to a certain extent and improve the waterproof performance of the pulp molding, but the adopted plastic film agent can influence the mechanical performance of the pulp molding, so that the strength and stiffness of the pulp molding are directly poor. Meanwhile, the poor combination property of the plastic film agent and the pulp molding material leads to poor waterproof property of the pulp molding material due to poor combination property of the plastic film agent and the outer surface of the fiber, and meanwhile, the plastic film agent has poor stability in gaps of a fiber network, and the waterproof property and the physical property of the pulp molding product are reduced in the long-time use or the exposed storage process, so that the due waterproof property and physical property cannot be maintained.
Further, the existing plastic film agent is poor in emulsion stability, improper in storage or easy to lose efficacy after long-term storage, and the performance improvement effect of the plastic film agent on pulp molding is directly reduced.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a hot water permeation prevention plastic film agent, a preparation method and application thereof in paper mold manufacturing, which can effectively prevent paper pulp molding from chipping, effectively prevent the plastic film agent from affecting the mechanical property of paper pulp molding while effectively improving the waterproof property of the paper pulp molding, further improve the strength and stiffness of the paper pulp molding, simultaneously improve the combination property of the plastic film agent and paper pulp molding materials, improve the overall stability of paper pulp molding products and further improve the long-term storage stability of the plastic film agent.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a process for preparing the plastic film agent for preventing the penetration of hot water includes such steps as preparing the basic material, preparing dripping liquid, and contact reaction.
The preparation method of the reaction base material comprises the steps of putting methacryloxyethyl trimethyl ammonium chloride DMC, methyl methacrylate and vinyl propionate into a reaction kettle, uniformly mixing, putting azodiisobutyronitrile, stirring and heating to 80-85 ℃, carrying out heat preservation and polymerization for 2-3h, adding deionized water, regulating pH to 5-6, putting an enhancement modifier, and stirring for 20-30min to obtain the reaction base material.
In the preparation of the reaction base material, the weight ratio of the methacryloxyethyl trimethyl ammonium chloride DMC, the methyl methacrylate, the vinyl propionate, the azodiisobutyronitrile, the deionized water and the reinforcing modifier is 18-20:80-85:2-2.5:0.2-0.23:105-110:14-15.
The reinforcing modifier is prepared by the following steps of preparing a compound, carrying out hydroformylation treatment and hyperbranched treatment;
The preparation method of the composite comprises the steps of putting zirconium nitrate pentahydrate, zinc nitrate hexahydrate, trimesic acid and polyvinylpyrrolidone into N, N-dimethylformamide DMF, stirring for 10-20min, continuously putting nano silicon dioxide with the average particle size of 10-20nm, performing ultrasonic dispersion for 5-10min to obtain a mixed dispersion liquid, putting the mixed dispersion liquid into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, putting the high-pressure reaction kettle into a constant temperature box, heating to 120-125 ℃, performing heat preservation reaction for 22-24h, naturally cooling, performing centrifugal separation to obtain a solid, washing 2-3 times by using deionized water with the weight of 4-5 times, and drying at 105-115 ℃ for 10-12h to obtain the composite.
In the preparation of the compound, the weight ratio of zirconium nitrate pentahydrate, zinc nitrate hexahydrate, trimesic acid, polyvinylpyrrolidone, N-dimethylformamide DMF and nano silicon dioxide is 10-11:3-3.3:8.2-8.6:6.5-7:330-350:60-65.
The hydroformylation treatment method comprises the steps of adding a compound into an ethanol solution (volume concentration is 85-90%) with the weight of 5-6 times, stirring for 10-20min, regulating the pH value to 5-5.5 by adopting anhydrous acetic acid, stirring and heating to 35-40 ℃, keeping the temperature and stirring and dripping N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane, controlling the dripping time of the N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane to 60-90min, continuing to keep the temperature and stirring for 4-5h after the dripping of the N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane is finished, separating a solid, washing with deionized water with the weight of 3-4 times, drying for 7-8h at 105-115 ℃ to obtain a modified intermediate, adding the modified intermediate into a glutaraldehyde aqueous solution (mass concentration of 1.2-1.5 wt%) with the weight of 9-10 times, stirring for 2-3h at room temperature, separating the solid, washing with deionized water with the weight of 4-5 times, and drying to constant weight of 105-115 ℃ to obtain the aldehyde modified intermediate.
In the hydroformylation treatment, the weight ratio of the compound to the N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane is 1:0.2-0.23.
The hyperbranched treatment method comprises the steps of putting an aldehyde modified substance into a reaction kettle containing absolute ethyl alcohol, stirring for 20-30min, completely replacing air in the reaction kettle by adopting nitrogen, stirring and heating to 65-70 ℃, preserving heat, stirring and dripping hyperbranched treatment liquid, controlling the dripping time of the hyperbranched treatment liquid to be 2-3h, continuing to preserve heat and stir for 2-3h after the dripping of the hyperbranched treatment liquid is finished, naturally cooling to room temperature, separating out solid substances, washing for 2-3 times by adopting absolute ethyl alcohol with the weight of 4-5 times, placing in a vacuum drying oven, and drying for 22-24h at the temperature of 30-35 ℃ in the vacuum degree of 0.085-0.095MPa environment to obtain the reinforcing modifier.
In the hyperbranched treatment, the weight ratio of the aldehyde modified substance to the absolute ethyl alcohol is 1:3-4;
the hyperbranched treatment fluid is an ethanol solution of dendritic polyamide-amine PAMAM, wherein the mass concentration of the dendritic polyamide amine is 8-8.5wt%, and the volume concentration of the ethanol solution is 50-55%;
The weight ratio of the aldehyde modified substance to the dendritic polyamidoamine in the hyperbranched treatment fluid is 1:0.25-0.3.
The method for preparing the dripping liquid comprises the steps of putting styrene, isooctyl acrylate, ethylene glycol dimethacrylate, diallyl dimethyl ammonium chloride and deionized water into a first batching kettle, stirring for 10-20min, continuously putting lauryl polyoxyethylene ether disodium sulfosuccinate salt into the first batching kettle, stirring and emulsifying for 30-40min to prepare a first dripping liquid for standby, putting sodium sulfite and deionized water into a second batching kettle, stirring and dissolving to prepare a second dripping liquid for standby.
In the preparation of the dripping liquid, in the first dripping liquid, the weight ratio of styrene, isooctyl acrylate, ethylene glycol dimethacrylate, diallyl dimethyl ammonium chloride, deionized water and laureth sulfosuccinic acid disodium salt is 45-50:4.5-5:2.3-2.5:7-8:80-85:0.8-1.2.
In the second dropping liquid, the weight ratio of the sodium sulfite to the deionized water is 6-6.5:100.
The contact reaction method comprises the steps of stirring and heating a reaction bottom material to 85-90 ℃, simultaneously dropwise adding a first dropwise adding liquid and a second dropwise adding liquid into the reaction bottom material, controlling the dropwise adding rate of the first dropwise adding liquid to be 6-7mL/min and the dropwise adding rate of the second dropwise adding liquid to be 0.5-0.6mL/min, stopping dropwise adding the second dropwise adding liquid after the dropwise adding of the first dropwise adding liquid is completed, carrying out heat preservation reaction for 2-3h, and naturally cooling to normal temperature to obtain the plastic film agent for preventing hot water permeation.
In the contact reaction, the weight ratio of the reaction primer to the first dropping liquid is 100:75-80.
A plastic film agent for preventing hot water from penetrating is prepared by the preparation method.
The application of the plastic film agent for preventing the hot water from penetrating in the paper mold manufacturing is that the plastic film agent for preventing the hot water from penetrating is mixed with pulp molding slurry, and then pulp molding is carried out;
Wherein the addition amount of the plastic film agent for preventing the hot water from penetrating is 1.5-1.8% of the weight of the pulp molding slurry.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention relates to a preparation method of a plastic film agent for preventing hot water permeation, which comprises the steps of adopting cationic monomer methyl acryloyloxyethyl trimethyl ammonium chloride DMC, acrylic ester monomer methyl methacrylate and nonionic monomer vinyl propionate to be matched in the preparation of a reaction base material, initiating pre-polymerization in the presence of azodiisobutyronitrile, uniformly mixing the reaction base material with a reinforcing modifier to prepare the reaction base material, adopting nano silicon dioxide as a matrix in the preparation of the reinforcing modifier, compounding a zinc doped zirconium-based metal organic frame with the nano silicon dioxide in an in-situ generation mode to prepare a compound, adopting specific bisaminosilane to carry out amination treatment on the compound in an hydroformylation treatment step to prepare a modified intermediate, adopting glutaraldehyde to carry out hydroformylation modification treatment on the modified intermediate to prepare the aldehyde modification product, adopting dendritic polyamide-amine PAMAM to carry out further hyperbranched modification treatment on the aldehyde modification product to prepare the reinforcing modifier, adopting styrene monomer, functional acrylic ester, crosslinking monomer and cationic dispersion monomer to carry out liquid adding in the step, preparing a first plastic film by dropwise adding the crosslinking agent, and the crosslinking agent, simultaneously forming a drop-contact polymer film in a second polymerization reaction end-side chain-containing polymer film in a long-phase contact stability-improving mode, and preventing the contact with a surface of the polymer film, the mechanical property of pulp molding is further improved through the reinforcing modifier and the combination and the filling effect of the reinforcing modifier on fiber network pores in the pulp molding, the physical barrier property is exerted, the moisture permeation is prevented, meanwhile, a compact crosslinked network is formed in the pulp molding raw material through the cooperation of the reinforcing modifier and the polymer, so that a compact waterproof coating is formed, the combination property of the plastic film agent and the fiber in the pulp molding is improved, the surface hydrophobicity of the fiber is enhanced, the film forming uniformity and the film layer stability of the plastic film agent on the outer surface of the fiber in the pulp molding are further improved, the overall stability of the pulp molding is further improved, the technical means are mutually matched and cooperate, the influence of the plastic film agent on the mechanical property of the pulp molding is effectively avoided while the water-proof property of the pulp molding is effectively avoided, the strength and the stiffness of the pulp molding are further improved, meanwhile, the combination property of the plastic film agent and the pulp molding material is improved, and the long-term storage stability of the plastic film agent is further improved.
(2) The pulp molding product prepared by adopting the hot water permeation prevention plastic film agent is free from powder falling and scraps after being mixed with pulp molding slurry, and has the tensile strength of 99.2-99.5Nm/g, the bursting index of 4.3-4.4 (kPa m 2)/g, the tightness of 1.38-1.41g/cm 3 and the tearing strength of 6.74-6.79 (mN m 2)/g.
(3) The plastic film agent for preventing hot water penetration is mixed with pulp molding slurry to prepare a pulp molding product (the thickness is 0.8mm, the quantitative amount is 400g/m 2), the Cobb value (120 s) is 12.4-12.7g/m 2, the water contact angle is 121-122 ℃, and 100 ℃ hot water is kept stand on the pulp molding surface for 70min without hot water penetration or diffusion.
(4) The hot water permeation prevention plastic film agent is mixed with pulp molding slurry to prepare a pulp molding product (the thickness is 0.8mm, the ration is 400g/m 2), the pulp molding product is exposed, kept stand and stored for 270 days in an environment with the temperature of 30 ℃ and the relative humidity of 75%, the waterproof film layer on the outer surface of the fiber is not separated or damaged in pulp molding, the tensile strength of the pulp molding product is 98.8-99.3Nm/g, the bursting index is 4.3-4.4 (kPa.m 2)/g, the tightness is 1.36-1.39g/cm 3, the tearing strength is 6.68-6.74 (mN.m 2)/g, the Cobb value (120 s) is 13.5-13.9g/m 2, the water contact angle is 120-121 DEG, and the pulp molding product is kept for 70min on the surface of the pulp molding without hot water permeation or diffusion.
(5) The hot water permeation prevention plastic film agent has no layering and precipitation after being stored for 180 days in an environment with the temperature of 35 ℃ and the relative humidity of 85 percent, the prepared paper pulp molding product (with the thickness of 0.8mm and the quantitative of 400g/m 2) has the tensile strength of 96.2-96.6Nm/g, the bursting index of 4.2-4.3 (kPa.m 2)/g, the tightness of 1.33-1.36g/cm 3, the tearing strength of 6.54-6.59 (mN.m 2)/g, the Cobb value (120 s) of 12.8-13.1g/m 2, the water contact angle of 119-120 DEG, and the 100 ℃ hot water is kept on the paper pulp molding surface for 70min without hot water permeation or diffusion.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
The embodiment provides a preparation method of a plastic film agent for preventing hot water permeation, which comprises the following steps:
1. Preparation of reaction primer
Adding methacryloxyethyl trimethyl ammonium chloride DMC, methyl methacrylate and vinyl propionate into a reaction kettle, uniformly mixing, adding azodiisobutyronitrile, stirring and heating to 80 ℃, carrying out heat preservation and polymerization for 2 hours, adding deionized water, regulating pH to 5, adding a reinforcing modifier, and stirring for 20 minutes to obtain a reaction base material.
Wherein the weight ratio of the methacryloxyethyl trimethyl ammonium chloride DMC, the methyl methacrylate, the vinyl propionate, the azodiisobutyronitrile, the deionized water and the reinforcing modifier is 18:80:2:0.2:105:14.
The reinforcing modifier is prepared by the following method:
1) Preparation of the composite
Putting zirconium nitrate pentahydrate, zinc nitrate hexahydrate, trimesic acid and polyvinylpyrrolidone into N, N-dimethylformamide DMF, stirring for 10min, continuously putting nano silicon dioxide with the average particle size of 10nm, performing ultrasonic dispersion for 5min to obtain mixed dispersion liquid, putting the mixed dispersion liquid into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, putting the high-pressure reaction kettle into a constant-temperature oven, heating to 120 ℃, preserving heat for 22h, naturally cooling, performing centrifugal separation to obtain a solid, washing with deionized water with the weight of 4 times, and drying at 105 ℃ for 10h to obtain the compound.
Wherein the weight ratio of zirconium nitrate pentahydrate, zinc nitrate hexahydrate, trimesic acid, polyvinylpyrrolidone, N-dimethylformamide DMF and nano silicon dioxide is 10:3:8.2:6.5:330:60.
2) Hydroformylation treatment
Adding the compound into ethanol solution (volume concentration is 85%) with 5 times of weight, stirring for 10min, regulating pH to 5 with anhydrous acetic acid, stirring and heating to 35 ℃, stirring and dripping N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane at room temperature, controlling dripping time of N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane to be 60min, continuing to stir at room temperature for 4h after dripping of N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane is finished, separating solid matters, washing with deionized water with 3 times of weight, drying at 105 ℃ for 7h to obtain modified intermediate, adding the modified intermediate into glutaraldehyde water solution (mass concentration is 1.2 wt%) with 9 times of weight, stirring at room temperature for 2h, separating solid matters, washing with deionized water with 4 times of weight, and drying at 105 ℃ to constant weight to obtain aldehyde modified matters.
Wherein the weight ratio of the compound to the N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane is 1:0.2.
3) Hyperbranched treatment
Adding the aldehyde modified substance into a reaction kettle containing absolute ethyl alcohol, stirring for 20min, completely replacing air in the reaction kettle by adopting nitrogen, stirring and heating to 65 ℃, preserving heat, stirring and dripping hyperbranched treatment liquid, controlling the dripping time of the hyperbranched treatment liquid to be 2h, continuously preserving heat and stirring for 2h after the dripping of the hyperbranched treatment liquid is finished, naturally cooling to room temperature, separating out solid substances, washing for 2 times by adopting absolute ethyl alcohol with the weight of 4 times, and drying to obtain the reinforcing modifier.
Wherein the weight ratio of the aldehyde modified substance to the absolute ethyl alcohol is 1:3.
The hyperbranched treatment fluid is an ethanol solution of dendritic polyamide-amine PAMAM, the mass concentration of the dendritic polyamide amine is 8wt%, and the volume concentration of the ethanol solution is 50%.
The weight ratio of the aldehyde modified substance to the dendritic polyamidoamine in the hyperbranched treatment fluid is 1:0.25.
2. Preparation of a drop solution
Adding styrene, isooctyl acrylate, ethylene glycol dimethacrylate, diallyl dimethyl ammonium chloride and deionized water into a first batching kettle, stirring for 10min, continuously adding lauryl polyoxyethylene ether sulfo succinic disodium salt, stirring and emulsifying for 30min to obtain a first dropwise adding solution, adding sodium sulfite and deionized water into a second batching kettle, stirring and dissolving to obtain a second dropwise adding solution, and standing by.
In the first dropping liquid, the weight ratio of styrene, isooctyl acrylate, ethylene glycol dimethacrylate, diallyl dimethyl ammonium chloride, deionized water and laureth sulfosuccinic acid disodium salt is 45:4.5:2.3:7:80:0.8.
In the second dropping liquid, the weight ratio of the sodium sulfite to the deionized water is 6:100.
3. Contact reaction
Stirring and heating the reaction bottom material to 85 ℃, simultaneously dripping the first dripping liquid and the second dripping liquid into the reaction bottom material, controlling the dripping speed of the first dripping liquid to be 6mL/min and the dripping speed of the second dripping liquid to be 0.5mL/min, stopping dripping the second dripping liquid after the dripping of the first dripping liquid is finished, preserving heat for 2 hours, and naturally cooling to normal temperature to obtain the plastic film agent for preventing hot water permeation.
Wherein the weight ratio of the reaction bottom material to the first dripping liquid is 100:75.
The product qualification test shows that the effective component content in the plastic film agent for preventing hot water permeation in the embodiment is more than 21wt%, the density (25 ℃) is less than 1.08g/cm 3, the viscosity (25 ℃) is less than or equal to 50 mPa.s, the pH (25 ℃) is in the range of 3.0-6.0, and the plastic film agent can be mixed with water in any proportion.
The embodiment also provides a plastic film agent for preventing hot water from penetrating, and the plastic film agent is prepared by adopting the preparation method.
The embodiment also provides an application of the heat-water-permeation-preventing plastic film agent in paper mold manufacturing, and the pulp molding is prepared after the heat-water-permeation-preventing plastic film agent is mixed with pulp molding slurry.
Wherein the addition amount of the plastic film agent for preventing the hot water from penetrating is 1.6 percent of the weight of the pulp molding slurry.
Example 2
The embodiment provides a preparation method of a plastic film agent for preventing hot water permeation, which comprises the following steps:
1. Preparation of reaction primer
Adding methacryloxyethyl trimethyl ammonium chloride DMC, methyl methacrylate and vinyl propionate into a reaction kettle, uniformly mixing, adding azodiisobutyronitrile, stirring and heating to 82 ℃, carrying out heat preservation and polymerization for 2.5h, adding deionized water, regulating pH to 5.5, adding a reinforcing modifier, and stirring for 25min to obtain a reaction base material.
Wherein the weight ratio of the methacryloxyethyl trimethyl ammonium chloride DMC, the methyl methacrylate, the vinyl propionate, the azodiisobutyronitrile, the deionized water and the reinforcing modifier is 19:83:2.2:0.21:107:14.6.
The reinforcing modifier is prepared by the following method:
1) Preparation of the composite
Putting zirconium nitrate pentahydrate, zinc nitrate hexahydrate, trimesic acid and polyvinylpyrrolidone into N, N-dimethylformamide DMF, stirring for 15min, continuously putting nano silicon dioxide with the average particle size of 15nm, performing ultrasonic dispersion for 8min to obtain mixed dispersion liquid, putting the mixed dispersion liquid into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, putting the high-pressure reaction kettle into a constant-temperature oven, heating to 123 ℃, preserving heat for reaction for 23h, naturally cooling, performing centrifugal separation to obtain a solid, washing 3 times by adopting deionized water with the weight of 4.5 times, and drying at 110 ℃ for 11h to obtain the compound.
Wherein the weight ratio of zirconium nitrate pentahydrate, zinc nitrate hexahydrate, trimesic acid, polyvinylpyrrolidone, N-dimethylformamide DMF and nano silicon dioxide is 10.5:3.2:8.5:6.7:340:62.
2) Hydroformylation treatment
Adding the compound into ethanol solution (volume concentration is 87%) with the weight of 5.5 times, stirring for 15min, regulating the pH value to 5.2 by adopting anhydrous acetic acid, stirring and heating to 38 ℃, stirring and dripping N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane at room temperature, controlling the dripping time of N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane to be 80min, continuing to stir for 4.5h with the temperature after the dripping of N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane is completed, separating out solid matters, washing with deionized water with the weight of 3.5 times, drying at 110 ℃ for 7.5h to obtain a modified intermediate, adding the modified intermediate into glutaraldehyde water solution (mass concentration of 1.3 wt%) with the weight of 9.5 times, stirring for 2.5h at room temperature, separating out solid matters, washing with deionized water with the weight of 4.5 times, and drying at 110 ℃ to constant weight to obtain the hydroformylation modified matter.
Wherein the weight ratio of the compound to the N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane is 1:0.22.
3) Hyperbranched treatment
Adding the aldehyde modified substance into a reaction kettle containing absolute ethyl alcohol, stirring for 25min, completely replacing air in the reaction kettle by adopting nitrogen, stirring and heating to 68 ℃, preserving heat, stirring and dripping hyperbranched treatment liquid, controlling the dripping time of the hyperbranched treatment liquid to be 2.5h, continuously preserving heat and stirring for 2.5h after the dripping of the hyperbranched treatment liquid is finished, naturally cooling to room temperature, separating out solid substances, washing for 3 times by adopting absolute ethyl alcohol with the weight of 4.5 times, and drying to obtain the reinforcing modifier.
Wherein the weight ratio of the aldehyde modified substance to the absolute ethyl alcohol is 1:3.5.
The hyperbranched treatment fluid is an ethanol solution of dendritic polyamide-amine PAMAM, the mass concentration of the dendritic polyamide amine is 8.2wt%, and the volume concentration of the ethanol solution is 52%.
The weight ratio of the aldehyde modified substance to the dendritic polyamidoamine in the hyperbranched treatment fluid is 1:0.28.
2. Preparation of a drop solution
Adding styrene, isooctyl acrylate, ethylene glycol dimethacrylate, diallyl dimethyl ammonium chloride and deionized water into a first batching kettle, stirring for 15min, continuously adding lauryl polyoxyethylene ether sulfo succinic disodium salt, stirring and emulsifying for 35min to obtain a first dropwise adding solution, adding sodium sulfite and deionized water into a second batching kettle, stirring and dissolving to obtain a second dropwise adding solution, and standing by.
In the first dropping liquid, the weight ratio of styrene, isooctyl acrylate, ethylene glycol dimethacrylate, diallyl dimethyl ammonium chloride, deionized water and laureth sulfosuccinic acid disodium salt is 48:4.7:2.4:7.5:82:1.1.
In the second dropping liquid, the weight ratio of the sodium sulfite to the deionized water is 6.2:100.
3. Contact reaction
Stirring and heating the reaction base material to 88 ℃, simultaneously dripping the first dripping liquid and the second dripping liquid into the reaction base material, controlling the dripping speed of the first dripping liquid to be 6.5mL/min and the dripping speed of the second dripping liquid to be 0.55mL/min, stopping dripping the second dripping liquid after the dripping of the first dripping liquid is completed, carrying out heat preservation reaction for 2.5h, and naturally cooling to normal temperature to obtain the plastic film agent for preventing hot water permeation.
Wherein the weight ratio of the reaction bottom material to the first dripping liquid is 100:77.
The product qualification test shows that the effective component content in the plastic film agent for preventing hot water permeation in the embodiment is more than 21wt%, the density (25 ℃) is less than 1.08g/cm 3, the viscosity (25 ℃) is less than or equal to 50 mPa.s, the pH (25 ℃) is in the range of 3.0-6.0, and the plastic film agent can be mixed with water in any proportion.
The embodiment also provides a plastic film agent for preventing hot water from penetrating, and the plastic film agent is prepared by adopting the preparation method.
The embodiment also provides an application of the heat-water-permeation-preventing plastic film agent in paper mold manufacturing, and the pulp molding is prepared after the heat-water-permeation-preventing plastic film agent is mixed with pulp molding slurry.
Wherein the addition amount of the plastic film agent for preventing the hot water from penetrating is 1.6 percent of the weight of the pulp molding slurry.
Example 3
The embodiment provides a preparation method of a plastic film agent for preventing hot water permeation, which comprises the following steps:
1. Preparation of reaction primer
Adding methacryloxyethyl trimethyl ammonium chloride DMC, methyl methacrylate and vinyl propionate into a reaction kettle, uniformly mixing, adding azodiisobutyronitrile, stirring and heating to 85 ℃, carrying out heat preservation and polymerization for 3 hours, adding deionized water, regulating pH to 6, adding a reinforcing modifier, and stirring for 30 minutes to obtain a reaction base material.
Wherein the weight ratio of the methacryloxyethyl trimethyl ammonium chloride DMC, the methyl methacrylate, the vinyl propionate, the azodiisobutyronitrile, the deionized water and the reinforcing modifier is 20:85:2.5:0.23:110:15.
The reinforcing modifier is prepared by the following method:
1) Preparation of the composite
Putting zirconium nitrate pentahydrate, zinc nitrate hexahydrate, trimesic acid and polyvinylpyrrolidone into N, N-dimethylformamide DMF, stirring for 20min, continuously putting nano silicon dioxide with the average particle size of 20nm, performing ultrasonic dispersion for 10min to obtain mixed dispersion liquid, putting the mixed dispersion liquid into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, putting the high-pressure reaction kettle into a constant-temperature oven, heating to 125 ℃, reacting for 24h under heat preservation, naturally cooling, centrifuging, washing with deionized water with the weight of 5 times of that of the solid, and drying at 115 ℃ for 12h to obtain the compound.
Wherein the weight ratio of zirconium nitrate pentahydrate, zinc nitrate hexahydrate, trimesic acid, polyvinylpyrrolidone, N-dimethylformamide DMF and nano silicon dioxide is 11:3.3:8.6:7:350:65.
2) Hydroformylation treatment
Adding the compound into ethanol solution (volume concentration is 90%) with 6 times of weight, stirring for 20min, regulating pH to 5.5 with anhydrous acetic acid, stirring and heating to 40 ℃, stirring and dripping N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane at room temperature, controlling dripping time of N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane to 90min, continuing to stir at room temperature for 5h after dripping of N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane is finished, separating solid matters, washing with deionized water with 4 times of weight, drying at 115 ℃ for 8h to obtain modified intermediate, adding the modified intermediate into glutaraldehyde water solution (mass concentration is 1.5 wt%) with 10 times of weight, stirring at room temperature for 3h, separating solid matters, washing with deionized water with 5 times of weight, and drying at 115 ℃ to constant weight to obtain the hydroformylation modified matter.
Wherein the weight ratio of the compound to the N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane is 1:0.23.
3) Hyperbranched treatment
Adding the aldehyde modified substance into a reaction kettle containing absolute ethyl alcohol, stirring for 30min, completely replacing air in the reaction kettle by adopting nitrogen, stirring and heating to 70 ℃, preserving heat, stirring and dripping hyperbranched treatment liquid, controlling the dripping time of the hyperbranched treatment liquid to be 3h, continuously preserving heat and stirring for 3h after the dripping of the hyperbranched treatment liquid is finished, naturally cooling to room temperature, separating out solid substances, washing for 3 times by adopting absolute ethyl alcohol with the weight of 5 times, and drying to obtain the reinforcing modifier.
Wherein the weight ratio of the aldehyde modified substance to the absolute ethyl alcohol is 1:4.
The hyperbranched treatment fluid is an ethanol solution of dendritic polyamide-amine PAMAM, the mass concentration of the dendritic polyamide amine is 8.5wt%, and the volume concentration of the ethanol solution is 55%.
The weight ratio of the aldehyde modified substance to the dendritic polyamidoamine in the hyperbranched treatment fluid is 1:0.3.
2. Preparation of a drop solution
Adding styrene, isooctyl acrylate, ethylene glycol dimethacrylate, diallyl dimethyl ammonium chloride and deionized water into a first batching kettle, stirring for 20min, continuously adding lauryl polyoxyethylene ether sulfo succinic disodium salt, stirring and emulsifying for 40min to obtain a first dropwise adding solution, adding sodium sulfite and deionized water into a second batching kettle, stirring and dissolving to obtain a second dropwise adding solution, and standing by.
In the first dropping liquid, the weight ratio of styrene, isooctyl acrylate, ethylene glycol dimethacrylate, diallyl dimethyl ammonium chloride, deionized water and laureth sulfosuccinic acid disodium salt is 50:5:2.5:8:85:1.2.
In the second dropping liquid, the weight ratio of the sodium sulfite to the deionized water is 6.5:100.
3. Contact reaction
Stirring and heating the reaction bottom material to 90 ℃, simultaneously dripping the first dripping liquid and the second dripping liquid into the reaction bottom material, controlling the dripping speed of the first dripping liquid to be 7mL/min and the dripping speed of the second dripping liquid to be 0.6mL/min, stopping dripping the second dripping liquid after the dripping of the first dripping liquid is finished, preserving heat for 3 hours, and naturally cooling to normal temperature to obtain the plastic film agent for preventing hot water permeation.
Wherein the weight ratio of the reaction bottom material to the first dripping liquid is 100:80.
The product qualification test shows that the effective component content in the plastic film agent for preventing hot water permeation in the embodiment is more than 21wt%, the density (25 ℃) is less than 1.08g/cm 3, the viscosity (25 ℃) is less than or equal to 50 mPa.s, the pH (25 ℃) is in the range of 3.0-6.0, and the plastic film agent can be mixed with water in any proportion.
The embodiment also provides a plastic film agent for preventing hot water from penetrating, and the plastic film agent is prepared by adopting the preparation method.
The embodiment also provides an application of the heat-water-permeation-preventing plastic film agent in paper mold manufacturing, and the pulp molding is prepared after the heat-water-permeation-preventing plastic film agent is mixed with pulp molding slurry.
Wherein the addition amount of the plastic film agent for preventing the hot water from penetrating is 1.6 percent of the weight of the pulp molding slurry.
Comparative example 1
The technical scheme of the embodiment 2 is adopted, and the difference is that 1) in the step of preparing the reaction base material, the addition of vinyl propionate is omitted, 2) in the step of preparing a compound is omitted, and the nano silicon dioxide with the same specification is directly used in the step of hydroformylation treatment.
Comparative example 2
The technical scheme of the embodiment 2 is adopted, and the technical scheme is that 1) the hyperbranched treatment step is omitted, the aldehyde modified substance prepared in the previous step is used as a reinforcing modifier in the step of preparing the reaction base material, and 2) the addition of isooctyl acrylate and diallyl dimethyl ammonium chloride in the first dropwise add solution is omitted in the step of preparing the dropwise add solution.
The addition amount of the hot water permeation preventing plastic film agent is controlled to be 1.6% of the weight of the pulp molding slurry, and the hot water permeation preventing plastic film agents of the examples 1-3 and the comparative examples 1-2 are respectively adopted to be mixed with the pulp molding slurry, and then the pulp molding is carried out to prepare the pulp molding product with the thickness of 0.8mm and the quantitative amount of 400g/m 2.
In the preparation process of pulp molding, the beating degree and the water retention value of the pulp after each plastic film agent preventing the penetration of hot water and the pulp molding pulp are mixed are detected. Meanwhile, the prepared pulp molded products are respectively placed in an environment with the temperature of 25 ℃ and the relative humidity of 50%, after standing for 24 hours, whether the pulp molded products have the conditions of powder falling and chip falling or not is observed, and the tensile strength, the burst index, the tightness and the tearing strength of the pulp molded products are detected.
And the water absorption performance, the wetting performance and the hot water permeation prevention performance of the pulp molding product are detected.
Wherein, the detection of the beating degree of the pulp is referred to the standard GB/T3332-2004 (Shobber-Ruigler method) for measuring the beating degree of pulp.
The detection of the water retention value of the pulp is referred to the standard GB/T29286-2012 determination of the water retention value of pulp.
The detection of tensile strength, bursting index, tightness and tearing strength of the pulp molded product refers to the standard GB/T12914-2018 of a constant speed tensile method (20 mm/min) for measuring tensile strength of paper and paper boards, GB/T454-2020 of a paper bursting strength measurement and GB/T455-2002 of a paper and paper board tear strength measurement.
The water absorption property of the pulp molded articles was measured by referring to the standard GB/T1540-2002 "measurement of water absorption of paper and paperboard (Wobbe method)", the Cobb value of each pulp molded article was basically measured by using a Cobb water absorption tester, and the water absorption test time was set to 120s.
The method for detecting the wettability of the pulp molded products comprises the steps of cutting each pulp molded product into flat test pieces with the size of 10mm multiplied by 15mm, fixing the flat test pieces on a glass slide by adopting double-sided adhesive tape, and measuring the water contact angle of deionized water on the outer surface of each test piece by utilizing a contact angle tester.
The detection of the heat water permeation resistance of the pulp molded products is carried out by referring to the standard GB/T36787-2018, namely, 100 ℃ hot water is absorbed by a glass suction tube, and is respectively dripped into each pulp molded product, and the pulp molded products are stood for 70 min, so that whether the hot water permeation phenomenon occurs in each pulp molded product is observed.
The specific results are shown in the following table:
Further, pulp molded articles (thickness: 0.8mm, basis weight: 400g/m 2) prepared by using the heat-water permeation preventing molding agents of examples 1 to 3 and comparative examples 1 to 2 were placed in an atmosphere having a temperature of 30℃and a relative humidity of 75%, and after the pulp molded articles were exposed and left to stand for storage for 270 days, whether or not the outer surface of the fiber waterproof film layer was peeled off or damaged during the pulp molding was observed, and the tensile strength, burst index, tightness, tear strength, water absorption property, wettability and heat-water permeation preventing property of each pulp molded article were examined, respectively. The specific results are shown in the following table:
Further, the heat-resistant water-permeable plastic films of examples 1 to 3 and comparative examples 1 to 2 were placed in an environment having a temperature of 35℃and a relative humidity of 85%, and after standing and storage for 180 days, it was observed whether delamination and precipitation occurred in each heat-resistant water-permeable plastic film, and each heat-resistant water-permeable plastic film was used for the preparation of pulp molded articles, and each of the pulp molded articles (thickness: 0.8mm, basis weight: 400g/m 2) was placed in an environment having a temperature of 25℃and a relative humidity of 50%, and after standing for 24 hours, the tensile strength, burst index, tightness, and tear strength of each pulp molded article were measured, and the water absorption property, wettability, and heat-resistant water-permeable property of each pulp molded article were measured.
The specific results are shown in the following table:
The preparation method of the plastic film agent for preventing the thermal water penetration comprises the steps of adopting cationic monomer methyl acryloyloxyethyl trimethyl ammonium chloride DMC, acrylic ester monomer methyl methacrylate and nonionic monomer vinyl propionate to be matched in the preparation step of preparing a reaction base material, initiating pre-polymerization in the presence of azodiisobutyronitrile, uniformly mixing the reaction base material with a reinforcing modifier to prepare the reaction base material, adopting nano silicon dioxide as a matrix in the preparation step of the reinforcing modifier, compounding a zinc doped zirconium-based metal organic frame with the nano silicon dioxide in an in-situ generation mode to prepare a compound, adopting specific bisaminosilane to carry out amination treatment on the compound in an hydroformylation treatment step to prepare a modified intermediate, adopting glutaraldehyde to carry out hydroformylation modification treatment on the modified intermediate to prepare an aldehyde modified object, adopting dendritic polyamide-amine PAM to carry out further hyperbranched modification treatment on the aldehyde modified object in the hyperbranched treatment step in the hyperbranched step, adopting styrene monomer, functional acrylic ester monomer, crosslinking and a crosslinking monomer to prepare a liquid adding mode, preparing a first plastic film by adding a crosslinking agent, preparing a polymer dropwise, and simultaneously, preparing a polymer film with high-side chain stability through the crosslinking agent dropwise contact, and the preparation step of the first plastic film can be carried out in a long-term storage stability, and the contact and the preparation of the polymer film can be carried out in a second polymerization step of the crosslinking film by adding the crosslinking agent to prepare a polymer film, the mechanical property of pulp molding is further improved through the reinforcing modifier and the combination and the filling effect of the reinforcing modifier on fiber network pores in the pulp molding, the physical barrier property is exerted, the moisture permeation is prevented, meanwhile, a compact crosslinked network is formed in the pulp molding raw material through the cooperation of the reinforcing modifier and the polymer, so that a compact waterproof coating is formed, the combination property of the plastic film agent and the fiber in the pulp molding is improved, the surface hydrophobicity of the fiber is enhanced, the film forming uniformity and the film layer stability of the plastic film agent on the outer surface of the fiber in the pulp molding are further improved, the overall stability of the pulp molding is further improved, the technical means are mutually matched and cooperate, the influence of the plastic film agent on the mechanical property of the pulp molding is effectively avoided while the water-proof property of the pulp molding is effectively avoided, the strength and the stiffness of the pulp molding are further improved, meanwhile, the combination property of the plastic film agent and the pulp molding material is improved, and the long-term storage stability of the plastic film agent is further improved.
According to the comparative example 1, the addition of a nonionic monomer is omitted, the compounding of a zinc-doped zirconium-based metal organic frame and nano silicon dioxide is omitted, a more complex and continuous compact waterproof polymer network structure cannot be formed through the interaction of the nonionic monomer and other raw material monomers (such as acrylate monomers and the like), the interface bonding performance of the plastic film agent and the pulp molding material cannot be further improved through the nonionic monomer, meanwhile, the filling and barrier effect on pulp molding pores cannot be realized through the cooperation of the zinc-doped zirconium-based metal organic frame and the nano silicon dioxide, the mechanical property and the waterproof property of pulp molding cannot be further improved, the possible microphase separation of the plastic film agent is avoided, the stability and weather resistance of the plastic film agent are improved, the possible microphase separation of the plastic film agent cannot be effectively avoided, and the long-term storage performance of the plastic film agent cannot be improved. The preparation method is characterized in that the water filtering performance of the pulp molding slurry is reduced in the preparation process, the mechanical properties (tensile strength, burst index, tightness and tearing strength) and the waterproof performance (120 s Cobb value, water contact angle and heat water permeation resistance) of the prepared pulp molding product are reduced to a certain extent, the overall stability of the prepared pulp molding product is reduced, the mechanical properties and the waterproof performance of the pulp molding product are reduced to a certain extent after the pulp molding product is exposed and stored for a long time, and the mechanical properties (tensile strength, burst index, tightness and tearing strength) and the waterproof performance (120 sCobb value, water contact angle and heat water permeation resistance) of the prepared pulp molding product are reduced to a certain extent after the plastic film agent is stored for a long time.
As can be seen from comparative example 2, the hyperbranched treatment step in the reinforcing modifier is omitted, and after the addition of isooctyl acrylate and diallyl dimethyl ammonium chloride in the first dropping liquid is omitted, only the hydroformylation modified product subjected to the hydroformylation modification treatment is reduced in bonding performance with the polymer raw materials in the plastic film agent, so that the mechanical property, the waterproof performance and the overall stability of the pulp molded product cannot be effectively improved, the long-term storage performance of the plastic film agent cannot be improved, and the waterproof performance of the plastic film agent cannot be further improved through the cooperation of the functional acrylate monomer and the cationic monomer in the first dropping liquid with other raw materials. The preparation method is characterized in that the water filtering performance of the pulp molding slurry is reduced in the preparation process, the mechanical properties (tensile strength, burst index, tightness and tearing strength) and the waterproof performance (120 sCobb values, water contact angle and heat water permeation resistance) of the prepared pulp molding product are obviously reduced, the overall stability of the prepared pulp molding product is reduced, the mechanical properties and the waterproof performance of the pulp molding product are obviously reduced after the pulp molding product is exposed and stored for a long time, and the mechanical properties (tensile strength, burst index, tightness and tearing strength) and the waterproof performance (120 s Cobb values, water contact angle and heat water permeation resistance) of the prepared pulp molding product are obviously reduced after the plastic film agent is stored for a long time.
The percentages used in the present invention are mass percentages unless otherwise indicated.
It should be noted that the above-mentioned embodiments are merely preferred embodiments of the present invention, and the present invention is not limited thereto, but may be modified or substituted for some of the technical features thereof by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
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| CN102630232A (en) * | 2009-09-17 | 2012-08-08 | 联合利华有限公司 | Use of branched addition copolymers in curing systems |
| CN106519871A (en) * | 2016-10-17 | 2017-03-22 | 铜陵市肆得科技有限责任公司 | Modified nanometer graphite reinforced water-based fluorocarbon antirust coating material for vehicle chassis, and preparation method thereof |
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| US6310116B1 (en) * | 1997-10-09 | 2001-10-30 | Kuraray Co., Ltd. | Molded polymer article having a hydrophilic surface and process for producing the same |
| US20100210745A1 (en) * | 2002-09-09 | 2010-08-19 | Reactive Surfaces, Ltd. | Molecular Healing of Polymeric Materials, Coatings, Plastics, Elastomers, Composites, Laminates, Adhesives, and Sealants by Active Enzymes |
| DE10338245A1 (en) * | 2003-08-20 | 2005-03-24 | Basf Ag | molding compound |
| JP2012500865A (en) * | 2008-08-21 | 2012-01-12 | イノーバ ダイナミクス インコーポレイテッド | Enhanced surfaces, coatings, and related methods |
| JP7077111B2 (en) * | 2018-04-10 | 2022-05-30 | 日本製紙株式会社 | Pulp mold |
| CN110607105A (en) * | 2019-08-06 | 2019-12-24 | 广州中国科学院工业技术研究院 | Water-based nano silicon-acrylic metal anticorrosive paint and preparation method thereof |
| CN115992452A (en) * | 2021-10-20 | 2023-04-21 | 大金工业株式会社 | water repellent composition |
| CN116289338B (en) * | 2023-03-08 | 2024-08-20 | 江西衡壤生态农业科技有限公司 | Production process of pulp molding product |
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| CN102630232A (en) * | 2009-09-17 | 2012-08-08 | 联合利华有限公司 | Use of branched addition copolymers in curing systems |
| CN106519871A (en) * | 2016-10-17 | 2017-03-22 | 铜陵市肆得科技有限责任公司 | Modified nanometer graphite reinforced water-based fluorocarbon antirust coating material for vehicle chassis, and preparation method thereof |
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